Halo-substituted phenoxyethyl carbamates and derivatives thereof



United States Patent U.S. Cl. 260-482 8 Claims ABSTRACT OF THE DISCLOSURE The compounds of the class halo-substituted phenyl oxyethyl esters of N-alkyl carbamic acids having the general formula wherein R and R are selected from the group consisting of hydrogen, lower alkyl having from 1 to 6 carbon atoms, inclusive, and lower alkenyl having from 2 to 6 carbon atoms, inclusive, at least one of R and R is a group other than hydrogen; and R is selected from the group consisting of nuclearly substituted phenyl, wherein said substituents are from 1 to 5 halogens, inclusive, especially chlorine; for example, 2,4-dichlorophenoxyethyl-N-methyl carbamate and 2,4,5-trichlorophenoxyethyl-N,N-di-n-propyl carb amate.

The compounds of the class are useful as preemergcnce and post-emergence herbicides. The compounds can be prepared by condensing a halophenyl oxyethanol and an alkyl isocyanate or condensing a halophenyl oxyethanol with an N,N-dialkyl carbamyl chloride.

This application is a continuation-in-part of my co pending application, Ser. No. 367,879, filed May 15, 1964, now abandoned.

This invention relates to certain new and novel organic compounds which may be used as herbicides. More specifically, this invention relates to certain substituted phenyl oxyethyl-N-alkyl carbamates and to the use of such compounds in herbicidal compositions.

The compounds comprising the instant class are esters of N-alkyl carbamic acids and correspond to the general formula wherein R and R are selected from the group consisting of hydrogen, lower alkyl having from 1 to 6 carbon atoms, inclusive, and lower alkenyl having from 2 to 6 carbon atoms, inclusive, at least one of R and R is a group other than hydrogen; and R is selected from the group consisting of nuclearly substituted phenyl, wherein said substituents are from 1 to 5 halogens, inclusive, especially chlorine.

3,439,021 Patented Apr. 15, 1969 "ice As examples of organic lower alkyl groups having from 1 to 6 carbon atoms which can be used for R and R are methyl, ethyl, propyl, butyl, and hexyl. Similarly, examples of lower alkenyl having from 2 to 6 carbon atoms are vinyl, allyl, iso-propenyl, Z-butenyl, 2-pentenyl, 1,3-butydienyl, and 2-hexenyl.

The compounds herein contemplated can be prepared by several methods. The monoalkyl carbamic acid derivatives were prepared by known methods, such as the reaction between the corresponding halo phenyl oxyethanol and an alkyl isocyanate. The addition of an organic base, such as triethylamine and the like, acts as catalysts to facilitate the completion of the reaction. The reaction proceeds readily in the liquid phase. The incorporation of an inert organic solvent is also useful, facilitating processing as well as agitation of the reactants. Temperatures that permit operation in the liquid phase and which are between room temperature and reflux temperature of the solvent, if any is used, are employed. Preferably the reaction mixture is refluxed, usually at an elevated temperature.

The dialkyl carbamic acid derivatives were prepared by the known reaction of an alcohol; e.g., a halo phenyl oxyalkanol with an N,N-dialkyl carbamyl chloride. In some instances it was found to be advantageous to use as a catalyst, such as cupric chloride, to increase the reaction rate. The reaction involved the use of a slight excess of carbamyl chloride, heated usually between C. to 100 C. with the desired aryloxy alcohol.

It has been found that the compounds of the present invention are particularly effective as herbicides. They are effective in the control of grasses and broadleaf plants with both pre-emergence and post-emergence activity.

The compounds of the present invention may be made in accordance with the following examples.

EXAMPLE 1 2,4-dichlorophenoxyethyl-n-methyl carbamate This example is representative of the preparation of monoalkyl carbamic acid derivatives within the embodiment of the present invention. In ml. of chloroform was dissolved 20.7 g. (0.1 M) of 2,4-dichlorophenoxyethanol with warming. Two drops of triethylamine were added as a catalyst thereby followed with the rapid addition of 6.8 g. (0.12. M) of methylisocyanate. The reaction mixture was then refluxed for three hours on a steam bath. The solvent and excess methylisocyanate were re moved on a steam bath with an air jet. The solid product, 2,4-dichlorophenoxyethyl-N-methyl carbamate, weighed 23.5 g. (89% of theory), M.P. 73-74" C.

Analysis calculated for C H Cl NO Chlorine 26.9% nitrogen, 5.3%. Found: chlorine, 26.7%; nitrogen, 5.0%.

EXAMPLE 2 2,4,5-trichlorophenoxyethyl-N,N-di-n-propyl carbamate This example is representative of the preparation of N,N-dialkyl carbamic acid derivatives of the present invention. In 11.4 g. (0.07 M) of N,N-di-n-propyl-carbamoyl chloride were dissolved by warming 12.1 g. (0.05 M) of 2,4,itrichlorophenoxyethanol. To the reaction mixture was added 0.1 g. of cupric chloride dihydrate and hydrogen chloride evolution began at once. The mixture was heated on the steam bath under an air condenser for two hours. Excess carbamoyl chloride was removed with an air purge. The product was taken up in benzene, washed with dilute hydrochloric acid followed by a water wash. After drying over anhydrous magnesium sulfate the product was filtered and the solvent removed on a steam bath with an air jet. The liquid product weighed 18.1 g. (98% of theory), n -=1.5218.

Analysis calculated for C H CI NO percent: C, 28.9; N, 3.8. Found: C, 28.7; N, 3.9.

The following is a table of the compounds prepared according to the aforedescribed procedures. Compound numbers have been assigned to each compound and are used throughout the balance of the application.

1 No. 1 prepared in Example 1. No. 9 prepared in Example 2.

As previously mentioned, the herein described novel compositions produced in the above described manner are phytotoxic compounds which are useful and valuable in controlling various plant species. The compounds of this invention were tested as herbicides in the following manner.

Pre-emergence herbicide test The seeds of crab grass, foxtail, water grass, Pigweed, Indian mustard and dock were planted in individual rows one-half inch deep in Santa Cruz sandy loam soil contained in compressed paper flats 8%" x 6%" which are 2%" deep. Enough seeds were planted to give about thirty to fifty plants each of the weed species in each flat. The flats were watered after planting. The following day each flat was sprayed at the rate of pounds of the candidate compound under test in '80 gallons of solution per acre. An atomizer was used to spray the solution on the soil surface. Two weeks later the degree of weed control was determined by comparing the amount of germination and growth of each weed in the treated flats with weeds in several untreated control flats. The results of this test are reported in Table II.

TABLE II.PRE-EMERGENOE ACTIVITY RATE, 20 LBSJA +=slight injury, ++=moderate injury, +++=severe injury or death Post-emergence herbicides test The seeds of crab grass, water grass, Indian mustard, dock and pinto bean were planted in individual rows as TAB LE III.POST-EMER GENCE ACTIVITY RATE, 12.5 LBSJA Compound Crab Water Indian Dock Pinto N 0. grass grass Mustard he on iii +=slight injury, +=moderate injury, +=severe injury or death.

The compounds of the present invention may be used as pre-emergence or post-emergence herbicides and may be applied in a variety of ways at various concentrations. In practice the compounds are formulated with an inert carrier, utilizing methods well known to those skilled in the art, thereby making'them suitable for application as dusts, sprays, or drenches. The amount applied will depend on the nature of the seeds or plants to be controlled and the rate of application may vary from '1 to 50 pounds per acre. One particularly advantageous way of applying the compounds is as a narrow band along a row crop, straddling the row.

Various changes and modifications may be made without departing from the spirit and scope of the invention described herein as will be apparent to those skilled in the art to which it pertains. It is accordingly intended that the present invention shall only be limited by the scope of the appended claims.

I claim:

1. The esters of N-alkyl carbamic acid corresponding to the formula wherein R and R are selected from the group consisting of hydrogen, lower alkyl having from 1 to 6 carbon atoms, inclusive, and lower alkenyl having from 2 to 6 carbon atoms, inclusive, at least one of R and R is a group other than hydrogen; and R is a nuclearly substituted phenyl group wherein said substituents are from. 1 to 5 chlorine atoms, inclusive.

2. A compound according to claim 1 wherein R hydrogen, R is methyl, and R is 2,4-dichlorophenyl.

3. A compound according to claim 1 wherein R ethyl, R is ethyl, and R is 2,4,5-trichlorophenyl.

4. A compound according to claim 1 wherein R is hydrogen, R is n-butyl, and R is 2,4,5-trichlorophenyl.

5. A compound according to claim 1 wherein R is n-butyl, .R is ethyl, and R is 2,4,5-trichlorophenyl.

6. A compound according to claim 1 wherein R is n-propyl, R is n-propyl, and R is 2,4-dichlorophenyl.

7. A compound according to claim 1 wherein R is hydrogen and R is lower alkyl having 1 to 6 carbon atoms, inclusive.

8. A compound according to claim 1 wherein R is lower alkyl having 1 to 6 carbon atoms, inclusive and R is lower alkyl having 1 to 6 carbon atoms, inclusive.

(References on following page) 5 v 6 References Cited FOREIGN PATENTS UNITED STATES PATENTS 253,656 12/ 1948 Switzerland.

2776196 1/1957 Gysin et a1. 260-479 LOR INE 4 ER ER 3,142,693 7/1964 Weiss et a1. 260 4ss 5 RA A WEINB G f Examm 3,238,036 3/1966 Heme 26%482 XR A. P. HALDUIN, Asszstant Exammer. 3,277,142 10/1966 Zerbe et a1. 260-455 USCLXR,

3,330,642 7/1967 Barron et a1. 260-479 X-R 71106 

